CN108117411A - The restorative procedure of ceramic oxygen-permeable membrane defect - Google Patents
The restorative procedure of ceramic oxygen-permeable membrane defect Download PDFInfo
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Abstract
The restorative procedure of ceramic oxygen-permeable membrane defect, comprises the following steps：At least one of the carbonate of Ca, Cu and Zn or oxide with preparing the component of ceramic oxygen-permeable membrane are mixed, ball milling, obtain powder I after drying sintering, powder I is taken to add in solvent ball milling again, centrifuge, drying obtains powder II.Dispersion liquid is made into after powder I is mixed according to a certain percentage with powder II, defective ceramic oxygen-permeable membrane is placed in above-mentioned dispersion liquid, is impregnated under vacuum, dry, sintering.The present invention provides a kind of restorative procedures of ceramic oxygen-permeable membrane defect, composite conductor oxygen-permeating film with perovskite structure or fluorite perovskite double structure is repaired, its using fusing point less than membrane material and with membrane material composition similar in material repaired, the defects of ceramic oxygen-permeable membrane generates in preparation process can be effectively repaired, so as to improve the utilization rate of oxygen permeation membrane and yield rate.
Description
Technical field
The invention belongs to ceramic material fields, and in particular to a kind of restorative procedure of ceramic oxygen-permeable membrane defect.
Background technology
Ceramic oxygen-permeable membrane is a kind of while has the inorganic ceramic membrane of oxygen conduction and electron conduction, is led in mixing
Oxonium ion is conducted by oxygen vacancies mechanism in body oxygen permeation membrane, and in order to maintain the charge balance of material internal, electronics is in oxygen flow
Reverse conduction in film is so not required additional circuit that can realize the circulate operation of oxygen permeation.Pass through this distinctive oxygen
Ion cavities mechanism carrys out conduction oxonium ion so that composite conductor oxygen-permeating film theoretically has 100% oxygen selective, therefore extensively should
For fields such as the energy, environment, chemical industry.
According to the structure of film, ceramic oxygen-permeable membrane can be divided into tubular film and laminar film.Traditional tubulose membrane preparation method
Mainly plastic extrusion method, this required equipment of method is simple, can prepare the membrane tube of random length, and can carry out
Batch production.This method needs ceramic powder and organic additive being prepared by mixing into the mud with some strength on pug mill
Stick, then by mud stick on tube extruding machine extrusion forming.It is possible that infiltrating gas and ceramic powder during mud stick is prepared
Particle easily causes the surface of membrane tube some acicular apertures occur during extrusion forming membrane tube, these aperture
Size is usually at 1 μm -50 μm, and these defects are inevitable during oxygen flow membrane tube is molded, which results in
On the one hand the phenomenon that membrane tube leaks air after sintering reduces the effective rate of utilization of membrane tube, on the other hand also results in membrane tube
Unnecessary waste.
In order to improve the oxygen permeability of oxygen permeable film material, loaded film prepared by curtain coating lamination pressure sintering is also research heat
Point.Tape casting refers to add in the ingredients such as solvent, dispersant, binding agent, plasticizer in ceramic powder, obtain finely dispersed
Slurry prepares a kind of forming method for requiring thickness thin film on casting machine.Since the method has, equipment is simple, can continuously grasp
The series of advantages such as work, production efficiency height, automatization level height, process stabilizing, therefore in the moulding process of ceramic material
To being widely applied.The film strips for being cast preparation can be obtained into the negative of different-thickness using the method for lamination hot pressing as required
Film carrier.For function separation layer thickness less than for 10 μm of loaded film, also tend to there are diaphragm can densified sintering product, but film
Surface has that some defects cause diaphragm gas leakage, this may be the uneven caused casting films band due to casting slurry
When the defects of occurring needle-like aperture, this also reduces the yield rate of loaded film to a certain extent, and limit loaded film should
With.
By comparing the moulding process of ceramic oxygen-permeable membrane, it is not difficult to find that either tubular film or laminar film, had been molded
Often inevitably it is present with defect in journey, this not only limits effective application of oxygen permeation membrane, and largely causes
The waste of oxygen permeation membrane.In consideration of it, the present invention provides a kind of powder with nano-scale for repairing defective ceramics thoroughly
Oxygen film, this method can effectively repair needle-like aperture, improve the effective rate of utilization and yield rate of ceramic membrane materials.
The content of the invention
Existing ceramic oxygen-permeable membrane, since the mixing in preparation process between ceramic powder and additive is uneven or burns
Knot technique be easy to cause defect, and defect mainly occurs with the aperture of needle-like, and size influences the application effect of film at 1 μm -50 μm
Fruit, the present invention is intended to provide a kind of restorative procedure of ceramic oxygen-permeable membrane defect, can have the defects of ceramic oxygen-permeable membrane
Effect ground is repaired, and improves the effective rate of utilization and yield rate of ceramic membrane materials.
The technical purpose of the present invention is achieved through the following technical solutions：
The technical purpose of the present invention is to provide the restorative procedure of ceramic oxygen-permeable membrane defect, comprises the following steps：
(1) at least one of the carbonate of Ca, Cu and Zn or oxide are mixed with preparing the component of ceramic oxygen-permeable membrane,
It adds in solvent and carries out ball milling mixing, be sintered after mixed powder is dried and obtain powder I, part powder I is taken to add in solvent ball again
Mill centrifuges, and drying obtains powder II；
(2) it is 1 according to mass ratio by powder I and powder II：0.5~10 mixing, is configured to dispersion liquid, by defective pottery
Porcelain oxygen permeation membrane is placed in above-mentioned dispersion liquid, is impregnated under vacuum, dry, sintering.
The present invention provides a kind of restorative procedure of ceramic oxygen-permeable membrane defect, to perovskite structure or fluorite-calcium titanium
The composite conductor oxygen-permeating film of ore deposit double structure is repaired, using fusing point less than membrane material and with membrane material composition similar in material
Expect to be repaired, the defects of ceramic oxygen-permeable membrane generates in preparation process can be effectively repaired, so as to improve oxygen permeation membrane
Utilization ratio and yield rate.
Description of the drawings
Fig. 1 is the schematic device for carrying out determination of gas tightness to repairing front and rear film in each embodiment and using,
Wherein, 1. entrance I, 2. entrance II, 3. outlet I, 4. export II, 5. sealing rings, 6. diaphragms to be measured.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The technical purpose of the present invention is to provide the restorative procedure of ceramic oxygen-permeable membrane defect, comprises the following steps：
(1) at least one of the carbonate of Ca, Cu and Zn or oxide are mixed with preparing the component of ceramic oxygen-permeable membrane,
It adds in solvent and carries out ball milling mixing, be sintered after mixed powder is dried and obtain powder I, part powder I is taken to add in solvent ball again
Mill centrifuges, and drying obtains powder II；
(2) it is 1 according to mass ratio by powder I and powder II：0.5~10 mixing, is configured to dispersion liquid, by defective pottery
Porcelain oxygen permeation membrane is placed in above-mentioned dispersion liquid, is impregnated under vacuum, dry, sintering.
In a specific embodiment, the ceramic oxygen-permeable membrane is with perovskite structure or fluorite-perovskite double structure
Composite conductor oxygen-permeating film, with the structure and composition shown in following expression：
Ba1-xSrxCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5),
La1-xSrxCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5),
BaCexFe1-xO3-δ(0 ﹤ x≤0.5),
La1-xSrxMnO3-δ(0 ﹤ x≤0.5),
Sm1-xSrxAl1-yFeyO3-δ(0 ﹤ x≤1,0 ﹤ y ﹤ 1),
Sm1-xSrxFeO3-δ(0 ﹤ x ﹤ 1),
Ce1-zSmzO2-δ-Sm1-xSrxAl1-yFeyO3-δ(0 1,0 ﹤ z≤0.5 of ﹤ x≤0.5,0 ﹤ y ﹤),
Ce1-ySmyO2-δ-Sm1-xSrxFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ y≤0.5)
Or Ce1-yGdyO2-δ-Gd1-xSrxFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ y≤0.5).
In a specific embodiment, the component for preparing ceramic oxygen-permeable membrane refers to each element involved in above-mentioned expression formula
Carbonate or oxide.
In a specific embodiment, when repairing the ceramic oxygen-permeable membrane with perovskite structure, Ca, Cu and Zn for being added in
Carbonate or oxide amount according to shown in following expression composition add in：
Ba1-x-zSrxMzCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5,0 ﹤ z≤0.5),
La1-xSrxCo1-y-zFeyMzO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5,0 ﹤ z≤0.5),
Ba1-zMzCexFe1-xO3-δ(0 ﹤ x≤0.5,0 ﹤ z≤0.5),
La1-x-zSrxMzMnO3-δ(0 ﹤ x≤0.5,0 ﹤ z≤0.5),
Sm1-x-zSrxMzAl1-yFeyO3-δ(0 1,0 ﹤ z≤0.5 of ﹤ x≤0.5,0 ﹤ y ﹤),
Sm1-x-zSrxMzFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ z≤0.5)
Wherein M is at least one of Ca, Cu and Zn；
When repairing the ceramic oxygen-permeable membrane with fluorite-perovskite double structure, the carbonate of Ca, Cu and Zn for being added in
Or the amount of oxide, in terms of Ca, Cu and Zn element, the doping in biphase ceramics oxygen permeation membrane is 1%~10%.
In above-mentioned restorative procedure, when repairing the ceramic oxygen-permeable membrane with fluorite-perovskite double structure, Ca, Cu and Zn
Doping of the element in biphase ceramics oxygen permeation membrane is preferably 1%~5%；More preferably 2~4%.
In a specific embodiment, those skilled in the art can be controlled for the first time with the time of empirically determined ball milling
I grain size of powder is milled to as 1~10 μm, is milled to II grain size of powder for the second time as 100~1000nm, is implemented as more specific
Mode, first time Ball-milling Time is 3~5h in the present invention, and time of second of II ball milling of powder is 30~50h.Twice during ball milling
Solvent used is ethyl alcohol.
In a specific embodiment, the rotating speed of the centrifugation is 5000~15000r/min, centrifugation time 10min
~30min.
In a specific embodiment, the solvent in step (2) used in dispersion liquid is water or organic solvent, and organic solvent is preferred
For ethyl alcohol, wherein powder I and II mixing quality of powder ratio are preferably 1:(0.5~4), the mass concentration of powder for 0.1%~
5%, it is preferably 0.1%~1%.Sintering temperature described in step (2) is 1100~1450 DEG C.
Describe the specific embodiment of the present invention in detail below in conjunction with technical solution and attached drawing.
In the examples below, determination of gas tightness is carried out using pressure application, test device such as Fig. 1 institutes to repairing front and rear film
Show.Diaphragm 6 to be measured is put into detection device, is sealed using sealing ring 5, sealing surface is towards entrance I 1, and I 3 is accessed in outlet
Precision pressure gauge blocks entrance II 2；High pure nitrogen is passed through toward entrance I 1, adjusts gas pressure.The airtight detection of diaphragm is examined
Measure whether mouthful II 4 has gas outflow, no gas outflow illustrates that diaphragm is fine and close；There is gas outflow to illustrate that diaphragm will not
Close, airtight degree can be represented with the gas flux of film.
Embodiment 1
It will be into being grouped into Ba0.5Sr0.5Co0.8Fe0.2O3-δDoughnut oxygen permeation membrane carries out air-leakage test, has filtered out
The membrane tube of defect.
(1) according to formula Ba0.33Sr0.33Ca0.33Co0.8Fe0.2O3-δIn, take each raw material according to the ratio of above formula：BaCO3、
SrCO3、CaCO3、Co3O4、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dries, sintering.Take out part powder
I adds in ethyl alcohol ball milling 50h again, and then 15000r/min centrifuges 15min, obtains powder II, dries.By powder I (grain size 1~
10 μm) with powder II (100~1000nm of grain size) according to mass ratio 1:1 mixing, as repair materials.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
Membrane tube one end silica gel seal of tube of defect, other end connection oil-free scroll vacuum pump vacuumize, make negative pressure is presented on the inside of membrane tube
State, by membrane tube be placed in more than in finely dispersed nano-powder ethanol solution, impregnate 3min.By the membrane tube after dipping in room temperature
1140 DEG C of sintering in Muffle furnace are put into after condition drying 12h.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 2.5 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 6.3 × 10-10mol cm-2s-1pa-1, prepared by explanation
Ba0.33Sr0.33Ca0.33Co0.8Fe0.2O3-δPowder can effectively repair the defects of oxygen permeation membrane, reduce its leakage rate.
Embodiment 2
It will be into being grouped into Ba0.5Sr0.5Co0.8Fe0.2O3-δLoaded film carries out air-leakage test, filters out defective film
Pipe.Wherein loaded film dense layer thickness is 7 μm, support layer thickness 0.5mm.
(1) according to formula Ba0.33Sr0.33Ca0.33Co0.8Fe0.2O3-δIn, take each raw material according to the ratio of above formula：BaCO3、
SrCO3、CaCO3、Co3O4、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dries, sintering.Take out part powder
I adds in ethyl alcohol ball milling 50h again, and then 15000r/min centrifuges 15min, obtains powder II, dries.By powder I (grain size 1~
10 μm) with powder II (100~1000nm of grain size) according to mass ratio 1:2 mixing, as repair materials.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
The loaded film of defect be placed in more than in finely dispersed nano-powder alcohol dispersion liquid, be placed in bottle,suction use water circulating pump together
It vacuumizes, loaded film is made to impregnate 3min under condition of negative pressure.Diaphragm after dipping is put into Muffle after room temperature condition dries 12h
1140 DEG C of sintering in stove.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 3.1 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 7.5 × 10-10mol cm-2s-1pa-1, prepared by explanation
Ba0.33Sr0.33Ca0.33Co0.8Fe0.2O3-δPowder can effectively repair the defects of oxygen permeation membrane, reduce its leakage rate.
Embodiment 3
It will be into being grouped into La0.6Sr0.4Co0.2Fe0.8O3-δDoughnut oxygen permeation membrane carries out air-leakage test, has filtered out
The membrane tube of defect.
(1) according to formula La0.6Sr0.4Co0.2Fe0.5Cu0.3O3-δIn, take each raw material according to the ratio of above formula：La2O3、SrCO3、
CuO、Co3O4、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dries, sintering.Part powder I is taken out again to add
Enter ethyl alcohol ball milling 50h, then 15000r/min centrifuges 15min, obtains powder II, dries.By powder I (1~10 μm of grain size) with
Powder II (100~1000nm of grain size) is according to mass ratio 1:2.5 mixing, as repair materials.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
Membrane tube one end silica gel seal of tube of defect, other end connection oil-free scroll vacuum pump vacuumize, make negative pressure is presented on the inside of membrane tube
State, by membrane tube be placed in more than in finely dispersed nano-powder ethanol solution, impregnate 3min.By the membrane tube after dipping in room temperature
1100 DEG C of sintering in Muffle furnace are put into after condition drying 12h.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 2.8 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 6.9 × 10-10mol cm-2s-1pa-1, prepared by explanation
La0.6Sr0.4Co0.2Fe0.5Cu0.3O3-δPowder can effectively repair the defects of oxygen permeation membrane, reduce its leakage rate.
Embodiment 4
It will be into being grouped into La0.6Sr0.4Co0.2Fe0.8O3-δThe loaded film of densified sintering product carries out air-leakage test, filters out
Defective diaphragm, wherein loaded film dense layer thickness are 7 μm, support layer thickness 0.5mm.
(1) according to formula La0.6Sr0.4Co0.2Fe0.5Cu0.3O3-δIn, take each raw material according to the ratio of above formula：La2O3、SrCO3、
CuO、Co3O4、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dries, sintering.Part powder I is taken out again to add
Enter ethyl alcohol ball milling 50h, then 15000r/min centrifuges 15min, obtains powder II, dries.By powder I (1~10 μm of grain size) with
Powder II (100~1000nm of grain size) is according to mass ratio 1:3.5 mixing, as repair materials.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
The loaded film of defect be placed in more than in finely dispersed nano-powder alcohol dispersion liquid, be placed in bottle,suction use water circulating pump together
It vacuumizes, loaded film is made to impregnate 3min under condition of negative pressure.Diaphragm after dipping is put into Muffle after room temperature condition dries 12h
1100 DEG C of sintering in stove.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 4.5 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 4.2 × 10-11mol cm-2s-1pa-1, prepared by explanation
La0.6Sr0.4Co0.2Fe0.5Cu0.3O3-δPowder can effectively repair the defects of oxygen permeation membrane, reduce its leakage rate.
Embodiment 5
It will be into being grouped into Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δTwo-phase doughnut oxygen permeation membrane carry out
Air-leakage test filters out defective membrane tube.
(1) according to formula 3wt%Zn-Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δ, taken respectively according to the ratio of above formula
Raw material：ZnO、CeO2、Sm2O3、SrCO3、Al2O3、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dry, burns
Knot.It takes out part powder I and adds in ethyl alcohol ball milling 50h again, then 15000r/min centrifuges 15min, obtains powder II, dries.
By powder I (1~10 μm of grain size) and powder II (100~1000nm of grain size) according to mass ratio 1:0.8 mixing, as reparation material
Material.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
Membrane tube one end silica gel seal of tube of defect, other end connection oil-free scroll vacuum pump vacuumize, make negative pressure is presented on the inside of membrane tube
State, by membrane tube be placed in more than in finely dispersed nano-powder ethanol solution, impregnate 3min.By the membrane tube after dipping in room temperature
1450 DEG C of sintering in Muffle furnace are put into after condition drying 12h.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 7.2 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 1.3 × 10-10mol cm-2s-1pa-1, prepared by explanation
3wt%Zn-Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δPowder can be repaired effectively the defects of oxygen permeation membrane, reduce
Its leakage rate.
Embodiment 6
It will be into being grouped into Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δLoaded film carries out air-leakage test, screening
Go out defective diaphragm.
(1) according to formula 3wt%Zn-Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δ, taken respectively according to the ratio of above formula
Raw material：ZnO、CeO2、Sm2O3、SrCO3、Al2O3、Fe2O3Mixing adds in ethyl alcohol and carries out ball milling 3h, obtain powder I, dry, burns
Knot.It takes out part powder I and adds in ethyl alcohol ball milling 50h again, then 15000r/min centrifuges 15min, obtains powder II, dries.
By powder I (1~10 μm of grain size) and powder II (100~1000nm of grain size) according to mass ratio 1:1.2 mixing, as reparation material
Material.
(2) more than repair materials by mass concentration are scattered in for 1% in ethyl alcohol, be uniformly dispersed in Ultrasound Instrument.To have
The loaded film of defect be placed in more than in finely dispersed nano-powder ethanol solution, be placed on together in bottle,suction and use recirculated water pumping
Vacuum makes loaded film impregnate 3min under condition of negative pressure.Then diaphragm is put into after room temperature condition dries 12h in Muffle furnace
1450 DEG C of sintering.
Air-leakage test is carried out to sintered membrane tube, the results show that before repairing the gas flux of oxygen permeation membrane for 3.1 ×
10-8mol cm-2s-1pa-1, the gas flux of the oxygen permeation membrane after reparation is 5.5 × 10-10mol cm-2s-1pa-1, prepared by explanation
3wt%Zn-Ce0.85Sm0.15O2-δ-Sm0.6Sr0.4Al0.3Fe0.7O3-δPowder can be repaired effectively the defects of oxygen permeation membrane, reduce
Its leakage rate.
Claims (9)
1. the restorative procedure of ceramic oxygen-permeable membrane defect, comprises the following steps：
(1) at least one of the carbonate of Ca, Cu and Zn or oxide with preparing the component of ceramic oxygen-permeable membrane are mixed, added in
Solvent carries out ball milling mixing, is sintered after mixed powder is dried and obtains powder I, part powder I is taken to add in solvent ball milling again, from
The heart separates, and drying obtains powder II；
(2) it is 1 according to mass ratio by powder I and powder II：0.5~10 mixing, is configured to dispersion liquid, by defective ceramics thoroughly
Oxygen film is placed in above-mentioned dispersion liquid, is impregnated under vacuum, dry, sintering.
2. restorative procedure according to claim 1, which is characterized in that the ceramic oxygen-permeable membrane be with perovskite structure or
The composite conductor oxygen-permeating film of fluorite-perovskite double structure, with the structure and composition shown in following expression：
Ba1-xSrxCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5),
La1-xSrxCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5),
BaCexFe1-xO3-δ(0 ﹤ x≤0.5),
La1-xSrxMnO3-δ(0 ﹤ x≤0.5),
Sm1-xSrxAl1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y ﹤ 1),
Sm1-xSrxFeO3-δ(0 ﹤ x ﹤ 1),
Ce1-zSmzO2-δ-Sm1-xSrxAl1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤1,0 ﹤ z≤0.5),
Ce1-ySmyO2-δ-Sm1-xSrxFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ y≤0.5),
Or Ce1-yGdyO2-δ-Gd1-xSrxFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ y≤0.5).
3. restorative procedure according to claim 2, which is characterized in that the component for preparing ceramic oxygen-permeable membrane refers to above-mentioned
The carbonate or oxide of each element involved in expression formula.
4. restorative procedure according to claim 1, which is characterized in that
When repairing the ceramic oxygen-permeable membrane with perovskite structure, the carbonate of Ca, Cu and Zn for being added in or the amount of oxide
It is added according to the composition shown in following expression：
Ba1-x-zSrxMzCo1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5,0 ﹤ z≤0.5),
La1-xSrxCo1-y-zFeyMzO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤0.5,0 ﹤ z≤0.5),
Ba1-zMzCexFe1-xO3-δ(0 ﹤ x≤0.5,0 ﹤ z≤0.5),
La1-x-zSrxMzMnO3-δ(0 ﹤ x≤0.5,0 ﹤ z≤0.5),
Sm1-x-zSrxMzAl1-yFeyO3-δ(0 ﹤ x≤0.5,0 ﹤ y≤1,0 ﹤ z≤0.5),
Sm1-x-zSrxMzFeO3-δ(0 ﹤ x ﹤, 1,0 ﹤ z≤0.5)
Wherein M is at least one of Ca, Cu and Zn；
When repairing the ceramic oxygen-permeable membrane with fluorite-perovskite double structure, the carbonate or oxygen of Ca, Cu and Zn for being added in
For the amount of compound in terms of Ca, Cu and Zn element, the doping in biphase ceramics oxygen permeation membrane is 1%~10%.
5. restorative procedure according to claim 1, which is characterized in that the grain size for being milled to powder I for the first time is 1~10 μ
M is milled to II grain size of powder as 100~1000nm for the second time.
6. restorative procedure according to claim 1, which is characterized in that first time Ball-milling Time be 3~5h, second of ball milling
Time for 30~50h, the solvent used in ball milling is ethyl alcohol twice.
7. restorative procedure according to claim 1, which is characterized in that the rotating speed centrifuged described in step (1) is
5000~15000r/min, centrifugation time are 10min~30min..
8. the preparation method according to claim 6 or 7, which is characterized in that the solvent in step (2) used in dispersion liquid is water
Or organic solvent, the mass concentration of powder is 0.1%~5%.
9. preparation method according to claim 1, which is characterized in that sintering temperature described in step (2) for 1100~
1450℃。
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